Basic azo dyestuffs containing a quaternized n-alkyl-n - beta-(imidazolyl) lower alkylarylamine group

ABSTRACT

A BASIC DYESTUFF OF THE FORMULA:   ((2-R2,3-Q,4-R3-IMIDAZOL-1-YL)-P-N(-R1)-B-N=N-)N-A (X)N(-)   WHEREIN: A IS A RESIDUE SELECTED FROM THE GROUP CONSISTING OF SUBSTITUTED AND UNSUBSTITUTED BENZENES, DIPHENYLS, DIPHENYLMETHANES, AZOBENZENES, THIAZOLES, BENZOTHIAZOLES, THIADIOZOLES, TRIAZOLES, AND DERIVATIVES THEREOF, WHEREIN THE SUBSTITUENTS ARE NON-WATER-SOLUBILIZING SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF CHLORINE, BROMINE, NITRILE, NITRO, ACETYL, TRIFLUOROMETHYL, LOWER ALKYLSULPHONYL, SULPHONAMIDE, MONO- AND DI-LOWER ALKYLSULPHONAMIDE, LOWER ALKOXYCARBONYL, ACETYLAMINE, PHENYLAMINE, PHENYL, LOWER ALKYL AND LOWER ALKOXY; B IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF SUBSTITUTED AND UNSUBSTITUTED PHENYLENE AND NAPHTHYLENE RADICALS BONDED TO THE AZO AND THE AMINO GROUPS IN THE 1- AND 4-POSITIONS, WHEREIN THE SUBSTITUENTS ARE NON-WATERSOLUBILIZING SUBSTITUENTS SELECTED FROM THE GROUP CONSISTING OF CHLORINE, METHYL, METHOXY AND ACETYLAMINO; R1 IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL HAVING FROM 1 TO 4 CARBON ATOMS, B-CYANOETHYL, B-HYDROXYETHYL AND BENZYL; R2 AND R3 EACH IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, METHYL, ETHYL AND PHENYL; P IS AN ALKYLENE RADICAL HAVING FROM 2 TO 3 CARBON ATOMS; Q IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL, BENZYL AND CARBAMOYLETHYL; X IS AN ANION; AND N IS 1 OR 2. THE DYESTUFFS OF THE PRESENT INVENTION ARE USEFUL AS DYES FOR A WIDE VARIETY OF MATERIALS, INCLUDING TANNED CELLULOSIC FIBERS, SILK, LEATHER, CELLULOSE ACETATE, PAPER, AND SYNTHETIC FIBERS, ESPECIALLY POLYMERIC AND COPOLYMERIC ACRYLONITRILE. THE DYESTUFF OF THE PRESENT INVENTION IS PARTICULARLY SUITABLE FOR DYEING POLYACRYLONITRILE FIBERS WITH EXCELLENT LIGHT, WET, AND HEAT-FASTNESS PROPERTIES.

UnitedStates Patent 3,592,806 BASIC AZO DYESTUFFS CONTAINING A QUATER-NIZED N-ALKYL-N p-(IMIDAZOLYL) LOWER ALKYLARYLAMINE GROUP Masao Iizuka,Kyokuii Arakawa, and Yoshiaki Yamamoto, Tokyo, Japan, assignors toHodogaya Kagalru Kabushiki Kaisha, Tokyo, Japan No Drawing. Filed Dec.12, 1967, Ser. No. 689,780 Claims priority, applies/M2137 3.lsapan, Dec.19, 1966, 8 Int. Cl. C0911 29/36, 62/82; D06p 1/02 US. Cl. 260-157 14Claims ABSTRACT OF THE DISCLOSURE A basic dyestulf of the formula:

wherein:

A is a residue selected from the group consisting of substituted andunsubstituted benzenes, diphenyls, diphenylmethanes, azobenzenes,thiazoles, benzothiazoles, thiadiozoles, triazoles, and derivativesthereof, wherein the substituents are non-water-solubilizingsubstituents selected from the group consisting of chlorine, bromine,nitrile, nitro, acetyl, trifluoromethyl, lower alkylsulphonyl,sulphonamide, monoand di-lower alkylsulphonamide, lower alkoxycarbonyl,acetylamino, phenylamino, phenyl, lower alkyl and lower alkoxy;

B is a radical selected from the group consisting of substituted andunsubstituted phenylene and naphthylene radicals bonded to the azo andthe amino groups in the 1- and 4-positions, wherein the substituents arenon-watersolubilizing substituents selected from the group consisting ofchlorine, methyl, methoxy and acetylarnino;

R is a member selected from the group consisting of lower alkyl havingfrom 1 to 4 carbon atoms, ,B-cyanoethyl, ,B-hydroxyethyl and benzyl;

R and R each is a member selected from the group consisting of hydrogen,methyl, ethyl and phenyl;

P is an alkylene radical having from 2 to 3 carbon atoms;

Q is a member selected from the group consisting of lower alkyl, benzyland carbarnoylethyl;

X is an anion; and

n is l or 2.

The dyestulfs of the present invention are useful as dyes for a widevariety of materials, including tanned cellulosic fibers, silk, leather,cellulose acetate, paper, and synthetic fibers, especially polymeric andcopolymeric acrylonitrile. The dyestuff of the present invention isparticularly suitable for dyeing polyacrylonitrile fibers with excellentlight, wet, and heat-fastness properties.

The present invention relates to new cationic dyestulfs. Moreparticularly, the present invention relates to new useful cationicdyestufis, which are preferably used wherein A represents a residue of adiazotizable primary aromatic or heterocyclic amine which may besubstituted by non-water-solubilizing substituents selected from thegroup consisting of chlorine, bromine, nitrile, nitro, acetyl,trifluoromethyl, lower alkylsulphonyl, sulphonamide, monoand di-loweralkylsulphonamide, lower alkoxycarbonyl, acetylamino, phenylamino,phenyl, lower alkyl and lower alkoxy, B represents a phenylene ornaphthylene radical bonded to the azo and amino groups in the 1- and4-positions, which may contain non-water-solubilizing substituentsselected from the group consisting of chlorine, methyl, methoxy andacetylamino, R represents a lower alkyl group having from 1 to 4 carbonatoms, or a substituted alkyl group selected from the group consistingof [i-cyanoethyl, fi-hydroxyethyl and benzyl, R and R each represents amember selected from the group consisting of hydrogen, methyl, ethyl andphenyl, P represents a linear or branched alkylene radical having from 2to 3 carbon atoms, Q represents a group selected from lower alkyl,benzyl and carbamoylethyl, X represents an anion equivalent to a cationand n represents 1 or 2.

The dyestuffs of the invention represented by the above Formula 1 can beprepared by coupling the diazonium or tetrazonium compounds derived fromaromatic or heterocyclic primary amines with the azo component of theFormula 2 (in which A, B, R R R P and n have the meanings definedabove), which can be prepared by coupling the With the (in which B R R Rand P have the meanings defined above), with a quaternizing agent.

In the aforementioned Formulas 1 and 2, the anion represented by X isequivalent to the cation and generally derived from a strong inorganicor organic acid, for example, from hydrochloric acid, hydrobromic acid,sulphuric acid, sulphuric acid monomethyl or ethyl ester, benzenesulphonic acid or toluene sulphonic acid. Chlorine, bromine,methosulphate, ethosulphate and p-toluene sulphonate ions are the mostpreferable anions. The aforesaid anions introduced into the dyestuffmolecule during the process may be exchanged for anions of otherinorganic acids, for example, phosphoric acid, sulphuric acid or anorganic acid, such as, formic acid, acetic acid, chloroacetic acid,oxalic acid, lactic acid or tartaric acid.

In certain cases free bases may be used. Often the production and use ofa double salt with inorganic salts is advantageous, in particular thezinc chloride double salt.

The residue of a diazotizable primary amine represented by A in theabove Formula 1 is derived from aromatic and heterocyclic amines such asanilines, benzidines, diarninodiphenylmethanes, arninoazo compounds,amino thiazoles, amino benzothiazoles, amino thiadiazoles, aminotriazoles and their derivatives. As specific examples of some suitablediazo components, there may be mentioned 2-chloro-4-nitroaniline,

p-nitroaniline,

2,4,5-trichloroaniline, 2,4,6-trichloroaniline,

p-amino acetophenone, 2-trifluorometyl-4-chloroaniline,2-ethylsulphonyl-S-trifluoromethylaniline,Z-methoxy--diethylamino-sulphonylaniline,2-chloro-4-methoxy-carbonylaniline, p-acetylaminoaniline,2-chloro-4-methylsulphonylaniline, 2-chloroaniIine- Lsulphonamide,4-amino-4'-methoxydiphenylamine, p-aminodiphenyl,

benzidine,

4,4-diaminodiphenylmethane,2-methoxy-4-(3'-nitrophenyl)azo-S-methylaniline,2,6-dichloro-4-nitroaniline, 2,4-dinitroaniline,2,4-dinitro-6-bromoaniline, 2-cyano-4-nitroaniline,2-rnethylsulphonyl-4-nitroaniline, 2,4-dicyano-6-chloroaniline,5-nitro-2-aminothiazole, 5-nitro-4-methyl-2-aminothiazole,3-phenyl-5-amino-1,2,4-thiadiazole, 2phenyl-5amino-1,3,4-thiadiazole,3-phenyl-5-amino-1,2,4-triazole, 6-cyano-2-aminobenzothiazole,o-chloro-2aminobenzothiazole, 4-methyl-6-nitro-Z-aminobenzothiazole,6-methylsulphonyl-2-aminobenzothiazole,6-acetylamino-2-aminobenzothiazole, 6-phenyl-2-aminobenzothiazole andthe like.

On the other hand, the the azo components described in theaforementioned Formulas 2 and 4 are amines of the benzene andnaphthalene series which are free from sulphonic acid and carboxylicacid groups, and which may contain substituents such as chlorine,methyl, methoxy or 4 acetylamino groups at any position except at thep-position to the amino group in ring B Suitable alkylene radicals,represented by p, are CH CH or As the substitutent R an alkyl radical,for example, a methyl, ethyl or butyl radical, a substituted alkylradical, for example, ,B-cyanoethyl, ,B-hydroxyl-ethyl or benzyl arepreferable. Both R and R are substitutents present on the imidazole ringbonded to P, and they can be methyl, ethyl or phenyl radicals.

The azo components of the Formula 4 are, for example, prepared byreacting a compound of the formula:

(in which B R and P have the meanings defined above, and Hal representsa chlorine or bromine atom) with an imidazole compound in the presenceof an alkali material.

Imidazole, 2-ethylimidazole, 2-phenylimidazole, 2,4-dimethylimidazole,2-ethyl-4-methylimidazole and especially 2-methylimidazole are suitablefor use as the imidazole compounds.

The following are representative of the azo components which may beemployed in production of the dyestutfs of this invention;

N-ethyl-N-fi- (2'-methylimidazolyl-1 ethylaniline, N-butyl-N-[B-(2'-methylimidazolyl-1' )ethylaniline,N-methyl-N-B-(2'-methylimidazolyl-1)ethylaniline, N-ethyl-N-fl-(2-methy1imidazolyl-1')ethyl-m-toluidine,N-methyl-N-fl-(2-methylirnidazolyl-1)ethyl-m-toluidine, N-methyl-N- 8-(2'-methylimidazolyl- 1 -N-acetyl-mphenylenediamine,N-ethyl-N-[i-(2-methylimidazolyl-1)ethyl-2-methoxy- S-methylaniline,N-[i-cyanoethyl-N-p- (2'-methylimidazolyl-1') ethylaniline,N-ethyl-N-fi- (2'-methylimidazo1yl-1')ethyl-unaphthylamine,N-methyl-N-p-(imidazolyl-1)ethylaniline, N-methyl-N-B- (imidazolyl- 1ethyl-m-chloroaniline, N-benzyl-N-fi- (irnidazolyl-l ethylaniline,'N-methyl-N-flimidazolyl- 1 pro pyl aniline, N-butyl-N-fi- (imidazolyl-1 ethyl-m-toluidine, N-methyl-N-fi- (imidazolyl-1')ethyl-m-toluidine,N-ethyl-N-fl-(2-ethylimidazolyl-1)ethyl-m-toluidine,N-fl-cyanoethyl-N-fl- 2',4-dimethylimidaz0lyl- 1' ethylaniline,N-B-hydroxyethyl-N-/3- (2'-ethyl-4-methylimid azolyl- 1' ethylaniline,and N-ethyl-N-p- (2-phenylimidazolyl-1')ethyl-m-toluidine.

The azo components of Formula 2 can be prepared by treating thecompounds of Formula 4 with a quaternizing agent. This procedure isalmost the same as where the dyestuffs of Formula 3 are treated with thequaternizing agent. Namely, this process is ordinarily carried out byheatlng the compounds of Formulas 4 and 3 with an alkylatlng oraralkylating agent in an inert organic solvent, such as benzene,toluene, xylene, chloroform, carbon tetrachloride, tetrachloroethane,chlorobenzene, o-dichlorobenzene, methanol, ethanol, dioxane,nitrobenzene or dimethyl formamide.

Instead of using the inert solvent, and excess of the alkylatmg oraralkylating agent may be employed.

Representative alkylating and aralkylating agents include alkyl halide,aralkyl halide or the alkylesters of sulphuric acid or an organicsulphonic acid. Examples of these materials are dimethylsulphate,diethylsulphate, benzene sulphonic methylester, p-toluene sulphonicmethylester, ethylor butylester, methylchloride, methylbromide,ethylbromide and benzyl chloride, which are preferably used.

Another excellent quaternizing method is to use an cap-unsaturatedcompound in an appropriate solvent in the presence of a proton. As thesolvent, ethanol, di methyl formamide, dioxane, formic acid or aceticacid is suitable, and as the proton, an inorganic acid such ashydrochloric acid, sulphuric acid or hydrobromic acid, or an organicacid such as glacial acetic acid, benzene sulphonic acid or toluenesulphonic acid is also suitable. Furthermore, as the a,p-unsaturatedcompound, acrylic amide, methacrylic amide, vinylketone or vinylethercan be used, and among them, acrylic amide is especially suitable.

The present reaction is in itself an exothermic reaction, but heating isnecessary to initiate the reaction. The reaction is preferably carriedout at an elevated temperature.

The azo coupling reaction of the invention can be carried by a knownmethod, for example, in a neutral to acidic aqueous medium, and ifnecessary, in the presence of a buffer agent such as sodium acetate orsodium-- carbonate. ,7

According to the invention, diazo dyestuffs are obtained by using anamine-containing azo group such as an aminoazo compound, or a diaminecapable of being tetraazotized such as those of the benzidine,diphenylmethane and heterocyclic series, wherein an equivalent amount ofthe azo component is used.

The dyestuff salts thus obtained are then readily separated from thereaction mixture by filtration, because of the precipitation in an inertorganic solvent. These sol- Stuff salts formed by the azo couplingreaction may be I recovered by filtration when they are precipitated, orthey may be salted out to precipitate by adding sodium chlo ride intothe reaction mixture, if desired. The resulting dyestuffs may beadvantageously purified by dissolving in hot water, and any impurematter can be filtered ofi as an insoluble residue. From the filtratethe dyestuff can be precipitated by adding sodium chloride. Zincchloride may be also added to form double salts which are recovered withease.

New basic dyestuffs obtained by the invention are soluble in water, andtheir aqueous solutions'are preferably applied for dyeing a very widevariety of materials, for. example, tanned cellulosic fibres, silk,leather, cellulose acetate, paper and synthetic fibres, especiallypolymeric and copolymeric acrylonitrile. Particularly, the new dyeandheat fastness properties.

stuffs dye polyacrylonitrile fibres with excellent light, wet

invention is not intended to be limited to them. Where not otherwisementioned, the parts and percentages are given therein as parts byweight and'percent by weight respectively.

EXAMPLE 1 A mixture of 17.3 parts of 2 chloro-4-nitroaniline, 47 partsof 36% hydrochloric acid and 110 parts of water is stirred at roomtemperature for 2 hours, and then cooled to 0 to 5 C. by the addition of130 parts of ice, and the amine is diazotized with a solution of 7 partsof sodium nitrite and 30 parts of water; After stirring for 1 hour, asmall amount of aminosulphonic acid is added to remove an excess ofnitrous acid present. The diazo solution is then run into a solution of36 parts of the compound of the formula:

. 6 in 400 parts of water and 150 parts of ice at 05 C. The whole isstirred for 1 hour, then 20.5 parts of sodium acetate are added. Afterthe coupling mass is stirred for several hours, 40 parts of sodiumchloride are added. The precipitated dyestuff is filtered off undersuction, and then dried. 47.8 parts of the dyestutf of the followingformula:

l CHzCH -N CHa ornso.

are obtained. The dyestuff salt is soluble with a red colour, and dyespolyacrylonitrile fibres from a weak dye bath in red shades which havegood light and wet fastness properties.

The same dyestulf is obtained by the following procedure. The diazoniumsalt solution prepared from 17.3 parts of 2-chloro-4-nitro-aniline usingthe procedure given in Example 1, is poured into a solution of 23 partsof the compound of the formula:

in 400 parts of water, parts of ice and 11 parts of hydrochloric acid,and stirred at 0-5 C. for 1 hour. Into the reaction mixture, a solutionof 19 parts of sodium carbonate in parts of water is added to bring thepH to about 5, and the whole is made alkaline by the addition of 40parts of a 10% sodium hydroxide solution,-and then 100 parts of sodiumchloride are added. The precipitated dyestuff is filtered off and dried.33 parts of the dyestuff having the following formula:

are obtained. 14.7 parts of dimethyl sulphate are added to a solution ofthe dyestutf in 600 parts of chloroform and the mixture is then boiledfor 2 hours under reflux. After cooling, the precipitate is filteredoff, and dissolved in 1000 parts of water, at 80 C., and clarified with1 part of active carbon. The dye salt is precipitated from the filteredsolution with 50 parts of sodium chloride, filtered and dried. Thedyestutf so obtained is equal to the one obtained before.

The azo component used is, for example, prepared as follows: 18.5 partsof N-ethyl-N-fl-chloroethylaniline are 8 This compound is treated with alittle excess of dimethyl sulphate in chlorobenzene at 95-l00 C. for 3hours to yield the quaternary compound of the formula:

In similar manner as in Example 1 using the starting materials shown inthe following table, dyestuffs are obtained which have similar dyeingproperties. In the right column of this table are given the shades ofcolour of the dyeing on polyacrylonitrile fibres.

Ex Diazo component Azo component Shade C2H5 Yellowish OzN NH2 Red.

I (IJH C H2CH2N\?NCHs C1 3 (Ill 3 63 Orange.

c1 NHz CH2CH2N NCH CH S 04 Cl 4 (31 04H 63 Yellow.

Cl- NH2 CH2CH2N NCII3 CHIIS O4 CH3 B Oran 0.

H 0 0 CNH F g CHzCHz-N NC2H5 01 V (3 F CH 6) Ycllowish Cl -NH: /CH2OH2CNorange.

3 CH GH -N NCH -l y 7 (131% CH; 63 Orange.

Q- NH CH CHgN N-CH C1 V S 0 C 2H5 8 (1 C Ha C 2 5 63 D 0.

-NI'I2 C 1138 O 4 9 H CH; C H2N /NCH a S O 2N (C 2H5) 2 \l/ 0 a Red.

H 0 0 O C- N H2 N/ Cl CH2CHz-N NCH3 C1 NHC O C H H3 J 10 "69 Red.

11 0 o CHN-Q-Nlh 1 /C2H5 N\ CH; s 04 CHzCHz-N N-CH3 C Ha Ex.- Diazocomponent Azo component Shade 11.. v i HaC OzS- NH2 CH2 63 Orange. v

. N Bfe x 1 Cl 1 CH2CH2N I\CzH i2"-.- 1 on ea B O2N NHZ F 2 s rown ClCH2CHz-N N CHaS O46 130.1 I o on o w H2No2s -NH 01120112011 3 rangeOH2CHz-N N-CHaJOHaSOfi /CH; 69 D0.

a CH -CH-W N-CHa CH3 69 Yellow.

CHzCHg-N N-C2H5 C2H5 S 049 CH3 Y CH:

- 0 11 e mange.

(J'HzOHz-N N-CH: CH S O 17 *1 Same as above 18 N01 (IJCH: .----d0------Orange.

EXAMPLE 19 This dyestulf salt is soluble in water with a reddish Asolution of 17.2 parts of 2,6-di'chloro-4-nitroaniline dissolved in 63parts of cone. sulphuric acid iscooled to C., and this is diazotizedwith nitrosyl sulphuric acid prepared from 5.8 parts of sodium nitrateand 87 parts of conc. sulphuric acid. After stirring at 8-100 C. for 2hours, the diazonium salt solution is poured into a solution of 31 partsof the compound of the formula:

| CHzOHzN N OHaSmQ in 220 parts of water and 5 80 parts of ice, and thewhole is stirred for 5.hours at less than 2 C. the dyestutf is saltedoutwith parts of sodium chloride, filtered, and then dried. 4.4 parts ofthe dyestufl of the following formula: 7

are obtained.

in 220 parts of water, 580 parts of ice and 9.5 parts of hydrochloricacid, and the whole is stirred at less than 2 C. for 2 hours. Into theresulting reaction mixture, 600 parts of ice are added, and further 200parts of a 40% sodium hydroxide solution are, added. After the couplingreaction is completed, parts of a 40% sodium hydroxide solution areadded to the mixture to make it 1 1 alkaline. The precipitate isfiltered off and then dried. 34 parts of the dyestufi having thefollowing formula:

71 parts of acrylic amide and 180 parts of glacial acetic acid at 60 C.After stirring at 90-95 C. for 3 hours, the whole is cooled to roomtemperature, and poured in to a solution of 600 parts of water and 250parts of ice. Into the resulting solution, the diazonium salt solutionprepared from 17.3 parts of 2-chloro-4-nitroaniline as in Example 1 isadded. After the coupling reaction is completed by the addition of 22parts of sodium acetate, the dye formed is salted out with 7.5 parts ofzinc chloride and 50 parts of sodium chloride, filtered and then dried.48.6 parts of the dyestuff of the formula:

is filtered off, and in order to purify the same, the raw r C2115product is dissolved in 550 parts of Water at 80 C. A small quantity ofinsoluble matter is separated by filtra- I L tion. This dyestufi isequal to the one obtained before. 1 CH1CH2 N\/ The azo component usedbefore is prepared by reacting I 2-methylimidazole with N ethylN-B-chloroethyl-m- 20 OH; toluidine in the presence of analkalinematerial. N-ethyl- 6B N-fl-(Z methylimadazolyl-l)ethyl-m-toluidine boilsat 214-215 C./ mm. Hg, which is then treated with di- 7 v methylsulphate to convert it into the quaternary salt. CHzCHzCONHz C1 56 ZnOhIn a similar manner as in Example 19, using the starting 25 materialsshown in the following table, dyestulfs are obtained which have similardyeing properties. In the right hand column are given the shades ofcolour of the dyeing on polyacrylom'trile fibres. are obtained.

Ex Diazo component Azo component shad 0 H5 G) Bluish OzN- -NH2 red.

N0 CHZCH2N N-CH; 0113s 04 21---. Br 04H '6; .Reddlsh J l Q I blue. 0 N--NH 2 Q 2 CH CHzCHzN N-CHa omsot N 02 a C CH: 69 Red. OzN- NH;

W ON CHzCHr-N N-OH; omsol I CH:

CHzCHzCN as Red. OzN- NHz SOzCH; CHzCHa-N N-CHa ole 24..." (Ill C2Hs G9Bordeau.

CN NH Q 2 5 CH2CH2N N-CH; [019 EXAMPLE This dyestufr' salt dissolvesquite readily in water, to give a red solution. It dyespolyacrylonitrile fibres in red shades which have excellent light andwet fastness properties.

EXAMPLE 26 A solution of nitrosyl sulphuric acid obtained from 7 partsof sodium nitrite and parts of cone. sulphuric acid is added to asolution of 15 parts of 5-nitro-2-aminothiazole in parts of 50%sulphuric acid at -5 C., and stirred at 5 C. for 4 hours.

. 13 r 1'4 Into the reaction mixture, a solution of 30 parts of themixture at -5 C. The reaction mixture thus obtained compound of theformula: is gradually poured to a solution of 3.6 parts of the com- 0 Hpound of the formula: 2 6 I CHzOHz-N NCHa 01 1 oHzcm- \/NCHa CH3SO46 in200 parts of water and 630 parts of ice is added, and 1} further stirredat less than 0 C. for 5 hours. Then sodium Ha hydroxide solution isadded to the mixture to neutralize it and the dye formed is precipitatedwith sodium chlom 40 parts of water and 30 parts of ice, and thenstirred E j fi and then dned' 39 parts of the dyestufi of for 1 hour. Asolution of 4.1 parts of sodium acetate in e mu parts of water is pouredto the mixture. After stirring OZN c H 9 for 10 hours, the dye formed isprecipitated with sodium 2 5 chloride, filtered and then dried. 4.5parts of the dyestufr of the formula:

omom-N N-GHa 01 Ha 20 s (1113 NC CZHE N=N N/ are obtamed.

This dyestuff salt dissolves quite readily in water to give CHfiCHZ areddish blue solution. It dyes polyacrylonitrile fibres a; in reddishblue shades which have excellent light and wet IL fastness properties.CHSSOfi In a similar manner as in Example 26, using the startingmaterials shown in the following table, dyestuffs are 013- E tainedwhich have similar dyeing properties. In the table, the shades on thepolyacrylonitrile fibres are shown in the right-hand column. areobtained.

Ex. Diazo component Azo component Shade 27-- O N -s CH; 7 s9 Reddish Ialue. H3O NH:

N CHzCHr-N N-CHzJ 0113s 0,

@- U I slNHz 0H OHgCfiz-U-CH; CH3S049 N-N /CzH as Red. QM

N112 s OHzOHz-N N-CHa 011 s 04 30. Same as aaove Yellowish QTN orange.

EXAMPLE 31 0.76 part of sodium nitrite is gradually added to 9.3 partsof conc. sulphuric acid, heated to C. to dissolve, cooled in ice-bath,and a mixture of acetic acid and propiom'c'acid (5:1 ratio) being freefrom water is added at less than 10 C.

To the resulting mixture, 1.8 parts of 6-cyano-2-aiminobenzothiazole isadded at 0-5" C., and further 12 parts of the same mixture of aceticacid and propionic acid is This dyestuif salt dissolves quite readily inwater to give a red solution. It dyes polyacrylonitrile fibres in redshades, which have excellent light and wet fastness properties.

In similar manner as in Example 31, using the starting materials shownin the following table, dyestuifs are obtained whcih have similar dyeingproperties. In the table, shades on polyacrylonitrile fibers are shownin right poured. After 3 hours, 0.8 part of urea is added to the column.

Ex. Diazo component Azo component Shade 32..... CH CH CN C1- S\ 2 2 69Red -NH2 N\ N CHzCHrN\/NCH3 CHaS O49 33.-- CH 1 i h N02 S\ a 69 B u 5red -NH2 N\ -N CHZGHZN N-CH; CH S 0,9

I on, I

H2CO2S s 2 5 W 69 Do.

l -N CH CH N N-CH; C1

CH3 N l 35 C H H COCHN -s 2 5 9 N [N112 N CHzCHr-N NCH3 CH S 0.1

3 Same as above Red.

%NH2 N What is claimed is: 2. A basic monoazodye as claimed in claim 1and hav- 1. A basic dyestuff of the formula: ing the formula:

/R1 Il a 89 R1 R3 AN=NBN I 9 A =NBN\ X N Q X R2 n 40 wherein A isselected from the group consisting of a benzene wherein: radical and asubstituted benzene radical wherein the A is a residue selected from thegroup consisting of substituted and unsubstituted benzenes, diphenyls,diphenylmethanes, azobenzenes, thiazoles, benzothiazoles, thiadiazoles,triazoles and derivatives thereof, wherein the substituents arenon-water-solubilizing substituents selected from the group consistingof chlorine, bromine, nitrile, nitro, acetyl, trifluoromethyl, loweralkylsulphonyl, sulphonamide, monoand di-lower alkylsulphonamide, loweralkoxycarbonyl, acetylamino, phenylamino, phenyl, lower alkyl and loweralkoxy,

B is a radical selected from the group consisting of substituted andunsubstituted phenylene and naphthylene radicals bonded to the azo andthe amino groups in the 1- and 4-positions, wherein the substituents arenonwater-solubilizing substituents selected from the group consisting ofchlorine, methyl, methoxy and acetylamino,

R is a member selected from the group consisting of lower alkyl havingfrom 1 to 4 carbon atoms, fi-cyanoethyl, ,B-hydroxyethyl and benzyl,

R and R each is a member selected from the group consisting of hydrogen,methyl, ethyl and phenyl,

P is an alkylene radical having from 2 to 3 carbon atoms,

Q is a member selected from the group consisting of lower alkyl, benzyland carbamoylethyl,

X is an anion and n is 1 or 2.

substituents are free from carboxyl and sulphonyl groups,

B is selected from the group consisting of substituted and unsubstitutedphenylene radicals bonded to the azo and the amino groups in the 1- and4-positions, wherein the substituents are free from carboxyl andsulphonyl groups,

R is a member selected from the group consisting of lower alkyl havingfrom 1 to 4 carbon atoms, {i-cyanoethyl, ,B-hydroxyethyl and benzyl,

R and R each is a member selected from the group consisting of hydrogen,lower alkyl and phenyl,

P is an alkylene radical having from 2 to 3 carbon atoms,

Q is a member selected from the group consisting of lower alkyl, benzyland carbamoyl ethyl, and X is an anion.

3. A basic monoazodye as in claim 2, wherein A is a substituted benzeneradical, the substituents being selected from the group consisting ofchlorine, bromine, nitrile, nitro, acetyl, trifluoromethyl, loweralkylsulphonyl, sulphonamide, monoand di-lower alkylsulphonamide, loweralkoxycarbonyl, acetylamino, phenylamino, phenyl, lower alkyl and loweralkoxy.

4. A basic monoazodye as in claim 2, wherein B is a substitutedphenylene radical, the substituents being selected from the groupconsisting of chlorine, methyl, methoxy and acetylamino.

5. A basic monoazodye as claimed in claim 1 and having the formula:

C2115 OzN N=N- N omen,- 01

I G9 N N-om crnsol 6. A basic monoazodye as claimed in claim 1 andhaving the formula:

7. A basic monoazodye as claimed in claim 1 and having the formula:

L I CHzC N-OHs CH CHSSO-l 8. A basic monoazodye as claimed in claim 1and having the formula:

lea omomN rL-omomoonm Ol MZnCl;

9. A basic monoazodye as claimed in claim 1 and having the formula:

wherein A is selected from the group consisting of substituted andunsubstituted thiazole and benzothiazole radicals, wherein thesubstituents are free from sulphonyl and carbonyl groups,

B is selected from the group consisting of a phenylene and a substitutedphenylene radical bonded to the azo and the amino groups in the 1- and4-positions, wherein the substituents are free from carboxyl andsulphonyl groups, R is a member selected from the group consisting oflower 5 alkyl having from 1 to 4 carbon atoms, fi-cyanoethyl,

;8-hydroxyethyl and benzyl, R and R each is a member selected from thegroup consisting of hydrogen, lower alkyl and phenyl, P is a memberselected from the group consisting of an alkylene radical having from 2to 3 carbon atoms, Q is a member selected from the group consisting oflower alkyl, benzyl and carbamoyl ethyl, and X is an anion.

01 omcmN N-cm 13. A basic monoazodye as claimed in claim 1 and havingthe formula:

omen;-

14. A basic monoazodye as claimed in claim 1 and having the formula:

CH3 CH3SO4G 313 References Cited UNITED STATES PATENTS 3,102,879 9/1963Baumann et al 260157 5 3,213,080 10/1965 Bloom et al. 260157X 3,216,99511/1965 Baumann et al. 260157 3,294,777 12/1966 Hansen et a1 2601573,349,096 10/ 1967 Rooney 260157X 3,409,606 11/1968 Lutz et al. 260157FLOYD D. HIGEL, Primary Examiner U.S. Cl. X.R.

